BOM-Phosphinite as an Electrophilic P-Stereogenic Transfer Reagent for the Synthesis of Bulky Phosphines: Synthesis of tert-Butyl(3,5-di-tert-butylphenyl)BisP*

Abstract

BOM-tert-butylmethylphosphinite borane is an efficient electrophilic P-stereogenic transfer reagent for the synthesis of bulky tertiary phosphines. The novel methodology relies on a one-pot deprotection/substitution on the trivalent phosphinite that takes place with very high stereospecificity. The potential of this strategy is demonstrated with the synthesis of a wide scope of tertiary phosphines in excellent enantiomeric excess. The methodology was applied to the synthesis of a bulky P-stereogenic BisP* ligand analogue.

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

“…The C 2 -symmetric P-stereogenic bisphosphorus ligands reported from 2001 to 2023 are shown in Figure , in the order of their publication years. ,− ,,,− A tetraphosphine ligand L41 and a C 3 -symmetric triphosphine ligand MT-Siliphos are also included in this figure as exceptions. All of these ligands possess unique structural and electronic properties, arising from the two different substituents on the phosphorus atoms and the ligand backbones, and exhibit their characteristic reactivities and stereoselectivities in various transition-metal-catalyzed asymmetric reactions.…”

Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes

“…91 It can be concluded that the phenyl/2-biphenylyl substituents of P 1 are probably not distinct enough and hence the introduction at this phosphorus of a bulkier aromatic group instead of 2-biphenylyl could be a strategy to explore future generations of the ligands. 92…”